Halogen-dibenzpyrenequinones and process of making same



lli

Patented Apr. 26, 1932 UNITED STATES PATENT OFFICE GEORG KR A NZLE-IN AND MARTIN GORELL, 0F HOOHST-ON-THE-MAIN, GERMANY, AS-

SIGNORS T0 GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE HALOGEN-DIBENZPYRENEQUINONES AND PROCESS OF MAKING SA ME No Drawing. Application filed March 5, 1926, Serial No. 92,586, and in Germany March M, 192.

The present invention relates to 1.6-dihalogen-dibenzpyrene-5.10-quinones, and to a process of preparing the same.

We have found that the halogen-dibenzpyrenequinon'es of the above given general formula are obtainable by treating a 1.5-dibenzoyl-2.G-dihydroxynaphthalene, the manufacture'of which is described in our copending application Ser. No. 92,585, filed March 5, 1926, with an agent which is capable of effecting an exchange of the two by droxy groups for chlorine and at the same time the closure of the ring to'the dibenzpyrenequinone. The halides of phosphorus, for instance, have proved to be suitable agents. It is advantageous to conduct the operation in such a manner that the dibenzoyldihydroxynaphthalene is suspended in a solvent and heated while adding, for instance, so much of phosphorus pentachloride as is necessary for effecting the exchange of the two hydroxy groups for halogen and the closing of the ring. There is first obtained a solution from which a well crystallized yellow intermediate-product soon separates which, after being isolated and heated in sulfuric acid of 66 B. strength to 80-1 90 0., is converted into the dichlordibenzpyrenequinone. The reaction most probably occurs according to the following equation:

Our new homogeneous halogen-dibenzpyrenetion. quinones possess similar tinctorial propertints.

ties as the non-substituted dibenzpyreneour invention:

"18 parts of 2.G-dihydroxy-1.5-dibenzoylnaphthalene are suspended in 50 parts of chlorobenzene and 44 parts of phosphorus pentachloride is added thereto. Reaction occursat once with heat andevolution ofhydrochloric acid. When the reaction is complete, the mass is heated to 100-110 C. so that the whole is at first dissolved whereupon the yellow intermediate-product soon separates with repeated evolution of hydrochloric acid. This intermediate-product is filtered by suction, washed and dried. It is insoluble when introduced in the cold into sulfuric acid of 66 B. strength, but when heated therein to 8090 C. it dissolves to a blue solution with a red hue. After the mixture has been agitated for a short time, it is poured on ice, filtered bysuction and washed benzene in yellow needles. The dyestuif dis-' solves in sulfuric acid to ,a pure violet solu- It dyes cotton from a red vat yellow mo Instead of 2.6-dihydroXy-1.5-dibenzoylpyrene-5.10-quinones of the following fornaphthalene, its derivatives, substituted in mula: the benzol residues, may be used and instead of phosphorus pentachloride other halides of phosphorus may be employed, such for inj 7 stance as phosphorus pentabromide or a mixture of phosphorus oxychloride and phosphorus-pentachloride. c e laim:

m 1. The process which comprises reacting 2.6 dihydroxy-1.5-dibenzoylnaphthalene with phosphorus pentachloride in the presence of cchlorobenzene' at a temperature of 15 about"100'-110 0., isolating the intermediate product thus obtained and treating it with sulfuric acid of about 66 B. strength at a temperature of about 8090 C.

2. The process which comprises reacting 20 1.5-dibenzoyl-2.G-dihydroxynaphthalenewith Wherem H Stand-S or'halogen. a halide of phosphorus and heating the re- In testlmony whereof, We afiix our slgna' sulting product with sulfuricacid. lures 3. In a process of preparing 1.6-dihalogen- GEORG KBANZLEIN- dibenzpyrene-5.10-quinone '-the step which MARTIN comprises reacting 1.5-dibenzoyl-26-dihydroXy-naphthalene with a halide of phos phorus. I

4. In a process of preparing 1.6-dihalo- 3O gendibenzpyrene 5.10 quinone the step which comprises reacting 1.5-dibenzoyl-2.6-

.dihydroxy-naphthalenewithphosphoruspentachloride.

5. In a process of preparing 1.6-diha1ogen- 5 dibenzpyrene-5.10-quinon e the step which comprises reacting 1.5-dibenzoyl-2.6-dihydroxy-naphthalene with'a mixture of phosphorus pentachloride and phosphorus oxychloride. 40 L6. Asanew product, the 1.6-dichlor-3A=-.8.9-

dibenzpyrenequinone of the following formula:

which forms a yellow powder which crystallizes from nitrobenzene in yellow crystalsand dissolves in sulfuric acid to a pure violet solu- 7. As new products 1i6-dihalogen-dibenz v 

